Lubricating compositions



Patented an 21, 1949 layer B. Goren, Brighton, Mata, anignor to Shell Development Company, San Francbco, Calif.,aoorporatlon of Delaware No Drawing.

This invention relates to new and novel products having properties of greatly improving and stabilizing lubricants. More particularly, this invention pertains to oleaginous materials, especially lubricants, such as mineral lubricating oils, synthetic lubricants of hydrocarbon and non-hydrocarbon origin and the like, containing a multi-functional additive having detergent and anti-ringsticking properties, as well as acting as an inhibitor of oxidation and corrosion.

It is well known that various lubricants, whether doped or undoped, tend to oxidize and form corrosive bodies and sludge when used in modern engines and machines operating under ordinary conditions, and especially at high speeds, elevated temperatures, heavy loads and other adverse conditions. Also as lubricants deteriorate during use, hard carbonaceous materials are formed on engine and machine parts, causing scratching and scufllng of movable metal parts and sticking" of valves and piston rings in engines. In addition, known lubricants are generally incapable of maintaining a continuous lubricating film between movable metal parts; this results in a gradual or rapid wearing away of the metal parts. The damage thus caused requires replacement of such parts, or even a complete overhauling of engines and machines, resulting in expensive loss of production and time.

In the case of the highest quality non-corrosive, stable undoped mineral lubricating oils, which are highly refined for specific uses, or synthetic lubricants developed for special uses, it has been found that such oils and lubricants are generally highly susceptible to oxidation and deterioration, becoming progressively more and more corrosive in engines and machines even under ordinary operating conditions.

To improve the lubricating properties of oils and synthetic lubricants, it has become the practice' to blend therewith one or more additives which have the effect or the property of inhibiting deterioration of lubricants and impart to them certain beneficial properties. Thus additives have been specifically designed which have the property of inhibiting corrosion of alloyed bearings such as copper-lead, cadmium silver and the like, developed for automotive, Diesel and aircraft engines. Acidic oxidation or decom- Application February 4, 1947, Serial No. 720,445 e 2: Claims. to]. 252-33.?)

positioncomponents rel-med in lubricants during use can readily attack these bearings, but are inhibited or prevented from doing this by the formation of a corrosion protective film formed with the aid of the additive .on the bearing surface. Additives have also been developed which possess the property of modifying the carbonaceous material formed by deterioration of lubricants on piston rods, rings and valves and other metal parts in internal combustion engines, automotive and truck engines, aviation engines, high speed Diesel engines, and the like.

These additives serve a very important function because by modifying this carbonaceous material so that it can be removed easily, the tendency of engine parts to become stuck is inhibited; ring sticking. Piston scuffing and scratching and wearing away of other parts and material reduction of engine efllciency is thereby prevented.

Other additives have been developed which act as detergents inorder to assist in the removal of soot, sludge, varnish, and/or lacquer formed from deterioration of the oil at high operating temperatures. Detergents, due to their cleansing action, prevent the build-up of these deleterious materials and assist in removing those formed.

Anti-wear additives have the property of reducing friction of movable metal parts of the same or different metals. Du to the function exerted or property imparted by such additives on lubrlcants, wear caused by direct frictional contact of metals can be greatly reduced. Also additives have been developed for withstanding extreme pressures, dispersion of impurities, solubilizing of certain other additives, etc.

The large number of additives thus developed has been due to the fact that an additive is capable of functioning mainly in only one specific manner: very few lubricant additives have the ability of improving a lubricant in more than just one respect. Thus, a good anti-oxidant vmight not be able to inhibit lacquer and varnish formation on piston rods, of to act as a detergent or corrosion inhibitor. In many cases, it is found that whereas an additive possesses very good properties in one respect, this same additive is the cause of harmful deposits in another respect. A second and third additive is therefore frequently required in order to obtain a good stable lubricant. The combination of additives in lubri-p synergistic effect is produced, resulting in a product of accentuated and improved properties. Another object of this invention is to add to mineral lubricating oils, synthetic lubricants, and the like, a multifunctional material so as to inhibit oxidation and corrosion and prevent the formation of sludge, varnish and lacquer in said lubricants even under adverse operating conditions. Still another object of this invention is to use in lubricating compositions a material which prevents ringsticking as well as the sticking of other engine parts due to deterioration of the lubricant. Also it is an object of this invention to use in lubricating compositions a material which inhibits wear, scufflng, scratching and other damage to engine parts. It is still another object of this invention to provide novel compounds which possess multifunctional improving and enhancing properties when added to lubricants.

The above and other objects may be attained in accordance with the present invention by adding to oleaginous materials, e. g. various lubricating bases, a minor amount of a reaction product obtained by treating phosphorus sulfide with saturated and unsaturated cyclic ketone fractions having at least 12 and preferably more than 18 carbon atoms in the molecule, said ketone fractions having been derived from isophorone bottoms during its synthesis from acetone by condensation as well as from other sources. Preferably, the phosphorus sulfides used to produce the reaction products of this invention should be selected from the class consisting of phosphorus pentasulfide, phosphorus heptasulfide and the like. The prepared ketones used to obtain the oil additive of this invention are the unsaturated cyclic ketones which are reacted with these phosphorus sulfides and .are normally obtained from isophorone bottoms produced by condensation of acetone under elevated temperature and pressure. The isophorone bottoms thus produced may be fractionated into various cuts each of which may be used to react with phosphorus sulfide to form the compound or oil additive of this invention. Among the specific isophorone fractions which may be used to form the reaction product of this invention are topped crude isophorone, topped crude hydrolyzed isophorone bottoms, and the like.. Although the mole ratio of the phosphorus sulfide and unsaturated cyclic ketones of this invention may be varied over wide limits, it is preferable to keep them within the range of from 1: 2 to 1:12, respectively. The reaction between these two ingredients is generally carried out under controlled elevated temperature conditions.

The terms topped. crude isophorone bottoms and topped crude hydrolyzed isophorone bottoms, and similar terms, which will be hereinafter used and fully described are generic and are used to identify various unsaturated cyclic ketone fractions of relatively high molecular weight obtained from acetone condensation. Unsaturated cyclic ketone fractions useable in reactions of the kind under consideration may be obtained by condensing acetone in 30% to 60% caustic solution at a temperature ranging between about 130 C. and 170 C., and under pressure of from 300 to 500 pounds per square inch. The resultant product is preferably subjected to distillation to remove distillable ketones and other constituents and impurities. The product remaining in the still is purified by filtration, solvent treatment, and comprises crude unsaturated cyclic ketones of high molecular weight, preferably referred to as crude isophorone bottoms. The term isophorone bottoms as referred herein is thus a complex mixture of high molecular weight unsaturated cyclic ketones containing at least 12 and preferably more than 18 carbon atoms in the molecule. The product formed is not to be confused with straight isophorone which is specifically 3,5,5 trimethyl cyclohexene-2-one-1, an unsaturated cyclic ketone containing only nine carbon atoms in the molecule. isophorone bottoms produced by condensation of acetone under conditions referred to above includes within its scope any and all unsaturated cyclic ketones containing at elast l2 and preferably more than 18 carbon atoms and having generally the chemical structural configuration of isophorone as well as the chemical structural configuration resulting from its condensation.

Crude isophorone bottoms can be fractionated and/or chemically treated and each fraction thereof can in turn be treated with phosphorus sulfide at elevated temperatures to produce a compound containing both phosphorus and sulfur. Among the various fractions which can be obtained from crude isophorone bottoms are topped crude isophorone bottoms which contain at least 15 carbon atoms in the molecular and which are obtained after removal of distillate from crude isophorone bottoms to a still head temperature of 140 C. at 10 mm. Hg pressure. Crude isophorone bottoms can be subjected to hydrolysis with dilute sodium hydroxide and the acetone and isophorone formed removed by distillation. The bottoms can then be filtered and purified and comprise essentially unsaturated cyclic ketones containing at least 12-and more carbon atoms in the molecule and are referred to as crude hydrolyzed isophorone bottoms. This material can be subjected to distillation to split it into two fractions. The distilled hydrolyzed isophorone fraction has a boiling point of about 140 C. at 10 mm. Hg pressure and'consists of a mixture of unsaturated cyclic ketones containing between 15 to' 18 carbon atoms in the molecule. The residue is referred to as topped crude hydrolyzed isophorone bottoms and is similar to topped crude isophorone bottoms. They comprise essentially unsaturated cyclic ketones of at least 15 carbon atoms in the molecule. Crude isophorone bottoms can be also subjected to condensation over solid sodium hydroxide to yield two types of resinous materials. The first resinous fraction or soft resin'has a viscosity at 210 F. of about 25-26 centistokes and an average molecular weight of 320 to 350. The heavier fraction or medium resin has a viscosity at 210 F. of about to centistokes and an average molecular weight of- 370 to 390. All of the various unsaturated cyclic ketone fractions obtained in th manner fully described above can be used for reacting with phosphorous sulfide to form a are preferred to others.

multi-iunctional lubricating additive. Other cyclic ketones having at least 12 carbon atoms are obtained by hydrogenating the above unsaturated cyclic ketones to obtain saturated cyclic ketones having at least 12 carbon atoms, alkyl cyclohexanone, i. e. dibutyl cyclohexanone, alkyl substituted carvomenthone, menthone, pulegone, carvone, camphor, and the like having at least 12 carbon atoms.

Phosphorus sulfides generally can be used in producing reaction products of this invention and preferably phosphorus pentasulfide and phosphorus heptasulfide are used because of their availability, cost and desired reactivity. The exact manner in which phosphorus and sulfur enter the reaction is at present not known or une derstood and the chemical structure of the reaction is also not known; however, it might be possible that thioketones containing phosphorus in the form of ester linkages are produced when phosphorus sulfide is reacted with saturated and/or unsaturated cyclic ketones. This is in contrast to early references of reactions of the type under discussion which stated that phosphorus did not enter the reaction and the products formed were thioketones. Thus A. E. Kretov and Ya. P. Komissarov in the Jr. Gen. Chem. U. S. S. R. 5, 388-91 (1935), state that the action of phosphorus pentasulfide on aliphatic ketones results in the formation of thioketones. Gatter.- man in Ber. 28, 2877, disclosed that when benzophenone in benzine solution is heated with phosphorus pentasulfide for several hours at 130 C.

in a bomb, thiobenzophenone forms and phosphorus does not enter into the reaction. Also Patents 2,309,829 and 2,402,640 disclose that ketones when reacted with phosphorus sulfide produce thioketones and phosphorus does not enter into the reaction. Unlike any previous teachings reaction products of this invention contain both phosphorus ,and sulfur, and physically as well as chemically are quite unlike in properties to thioketones.

The phosphorous sulfide cyclic ketone reaction products of this invention can be prepared from any of the ketone fractions obtained in the manner described above, although certain fractions The kind of phosphorus sulfide used, the ratio of the two reactants, the temperature, time and conditions under which the reaction is carried out, as well as the manner in which the final product is recovered, are also important and controlling factors. The preferred ketone fractions are topped crude isophorone bottoms which are residues remaining after removal of distillate from crude isophorone bottoms to a still head temperature of 140 C. at mm. Hg pressure, and comprise unsaturated cyclic ketones containing at least 15 carbon atoms in the molecule. Another preferred fraction is topped crude hydrolyzed isophorone bottoms obtained from crude hydrolyzed isophorone bottoms similar to the topped crude isophorone bottoms. The term topped used throughout has the same meaning as in the petroleum art, namely a distillation or fractionation step, whereby certain materialsare removed as an overhead fraction.

Phosphorus pentasulfide and phosphorus heptasulfide are preferred although other phosphorus sulfides can be used. The mol ratio of phosphorus sulfide to ketone is a most important factor in obtaining a desired reaction product. When the mol ratio of phosphorus sulfide to ketone is from 1:2 to 111.2, superior reaction products are obtained. However, this mol ratio need not be adhered to strictly and may be varied at times to 1:4 and even 1:8 of phosphorus sulflde to ketone. respectively. Generally, when these ratios are used the resultant products are relatively inferior and for some lubricants may prove to be unsatisfactory.

The reaction temperature can be varied between about 130 C. and about 200 C. or higher, and preferably between 150 C. and 170 C. However, the initial or starting temperature should be controlled quite carefullyand be restricted within relatively rather narrow limits to obtain a desired controlled reaction. If initially the reaction is allowed to progress at 'a. rapid rate over 100 C., due to the vigor of the resultant reaction, it cannot then be controlled and an undesirable product forms. The initial stage of the reaction should be carefully controlled and heated slowly in a suitable bath or by any suitable means to an initial temperature of between about C. and 80 C., and thereafter heated relatively more rapidly to the desired or optimum temperature.

The reaction should be carried out in substantially inert atmosphere and the two materials can be reacted per se or dispersed-in a suitable inert or non-reactive diluent and then reacted under conditions described above. When the reaction is completed, the desired fraction can be extracted with a'suitable material, such as nonaromatic hydrocarbons, e. g. one having a boiling range of between 164 F. to 233 F., or an aviation base stock gasoline boiling up to 190 F. and containing little, e. g. not more than about 4%, aromatics.

The preparation of phosphorus sulfide with saturated or unsaturated cyclic ketone reaction products of this invention is relatively simple and requires no elaborate or special equipment, undue precautions or skill. The obtainment of the desired reaction products simply requires a mixing and stirring of cyclic ketones of this invention with for example dry, powdered phosphorus pentasulfide, in an inert atmosphere, such as nitrogen or carbon dioxide, for 2 to 8 hours. Initially, the reaction is kept at between about 60 C. and about C., the mixture being then rapidly heated to an elevated temperature of 200 C., or higher. At the completion of the reaction the desired fraction may be extracted with a nonaromatic hydrocarbon having a boiling point of 164 F. to 233 F. The non-extractable material is discarded and the solution is filtered, evaporated at steam temperature ina current of inert gas to yield the desired products suitable as lubricant additives. The additives thus produced vary in color from amber to dark brown and in consistency from viscous liquid to brittle solids. They are readily soluble in various petroleum lubricating oils as well as other types of oleaginous materials, oils and synthetic lubricating bases.

To more clearly illustrate the present invention, the following examples are presented. It is to be understood, however, that various modifications can be resorted to without departing from the spirit of the invention as presented in the subjoined claims.

EXAMPLE I A mixture of 32 mols of cyclic unsaturated ketones containing at least 18 carbon atoms in the molecule, obtained by topping bottoms from crude isophorone bottoms at a kettle temperature of C. and 10 mm. Hg pressure, and 0.22 mol 7 of phosphorus pentasuirlde was stirred and heated in an inert atmosphere of carbon dioxide for approximately five hours at around about 160 C. The mixture was placed initially in a bath maintained at about 60 C. to 80 C., and then rapidly heated to 160 C. At the end of the reaction period, the desired product was extracted with a non-aromatic hydrocarbon having a boiling range of between about 164 F. and 233 F. The solution was filtered and the filtrate evaporated at steam temperature in a current of carbon dioxide. The resultant product-on analysis contained 17.4% sulfur and 5.7% phosphorus.

Exhaust: 11

EXAMPLE III The procedure followed was exactly the same as in Example 1, except that the mol ratio of ketone to phosphorus pentasulfide was varied, 0.32 to 0.05 mol, respectively, of each additive being used. The final product on analysis contained 7.7% sulfur and 0.82% phosphorus.

EXAMPLE IV The same mixture as used in Example I was employed and was reacted under the same conditions, except that the mol ratio of ketone to phosphorus pentasulfide was 0.32 to 0.17. The final product on analysis contained 17.0% sulfur and 4.1% phosphorus.

Exams: V

A mixture of 1.6 mols of ketones as used in Example 1 and 0.54 mol of P481 was reacted and the reaction product was isolated in the usual manner as described in the above examples. The final product contained 14.3% sulfur and 5.2% phosphorus.

In each of the first four examples all materials and conditions were kept the same except that in each case the mol ratio of ketone to phosphorus pentasulfide was varied. Although in each case the oxidation stability of a mineral lubricating oil was greatly improved the best results were obtained when the mol ratio of ketone to phosphorus sulfide was maintained close to 2: 1. This is evident from the following table:

Teens I Oxiodation stability determinations A refined, undoped lubricating oil, having a viscosity of 120-125 S. U. at 210 F., was employed; the oxidation was effected at 150 C.

1 All oxidation products corrected to 1800 ml. oxygen absorbed/100 oil, assuming amount of product is proportioned to oxygen ebsor To show the synergistic effect reaction products of this invention have on compounded lubricants, oxidation stability determinations were carried out on a number of outstanding lubricants and the results were as follows:

Tut: II

Oxidation stability d termination A refined, undoped lubricating oil, having a viscosity of 64-67 S. U. at 210 F., was employed; oxidation at 150 C.

A1] oxidation products corrected to 1800 ml. oxygen absorbed] 1%0 g. b23131, assuring amount of product is proportioned to oxygen a sor The additives of this invention were tested alone and together with various lubricating oil additives in the multiple four-ball machine similar in principle to the Boerlage apparatus described in the magazine, Engineering, volume 136,. July 14, 1933. This apparatus comprises four steel balls arrangedin pyramid formation. The top ball is rotated by spindles against the three bottom balls which are clamped in a stationary ball holder. The halls are immersed in the oil to be tested. Tests were run for two hours at 700 R. P. M. under '7 kg. load and at a controlled temperature of 130 C. The diameter of the wear scars worn on the three balls from the base of the pyramid were measured, and the average taken as the true indication of wear.

TABLE III Wear evaluation in the multiple four-ball machine A refined, undoped lubricating oil, 64-67 S. U. at 210 F. was employed.

The doped and undoped oils were then further tested by a test known as the thrust bearing corrosion test (described in the National Petroleum News, September 1'7, 1941, pp. R-294-296) which is carried out as follows: A hardened steel disc is made to rotate for 20 hours under constant pressure against three fiat copper-lead bearings.

The bearings assembly rests in a steel cup filled with the oil to be tested and the temperature of the oil is maintained at a predetermined figure by thermostatic control. The bearings are weighed before and after the test, the difference in weight 7:, representing the loss sustained during the test.

duration, 125 p.s.i. Thrust,2400-R. P. M. A rethe reaction product and preferably only between I combined with other additives in lubricants, such as, bloomingagents, pour point depressants, vistergents which include oil-soluble salts of various alkyl substituted salicylic acids, phthalic acid and i 2.4 am

I I'm: I Testsinthrastbemng machine Fixed conditions: Cu-Pb bearings, 20 hours dined, undoped, commrcial lubricating oil 8.1!. at 210 1". was employed.

tageously in the amount of about 0.025% to 0.2% sulfate Also'alkaline metal salts of alkyl phenol-aldehyde condensation reaction. products are excellent detergents.

ple, alkyl phenols such as 2,4,6 trimethyl phenol,

.The reaction products'of this invention can be used as valuable additives to or constituents of heavy duty oils, motor oils, Diesel oils, aviation oils, synthetic oils, and the like, because of their anti-corrosion, antioxidation, and anti-wear properties. The amount of additive used can be varied over relatively wide limits but'generally it is not necessary to use more than 5 by weight of about 0.1% to 2.0% by weight is added to base lubricants.

The reaction product of this invention can be cosity improvers, extreme pressure agents, anti- I foaming agents, and the like. Among the specific additives which can be used are oil-soluble debases. with detergent-forming acids. Such bases include metal as well as organic bases. Metallic bases include the hydroxides, etc. of the alkali metals, Cu, Sr, Ba, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, G0, etc. Organic bases include various nitrogen bases as primary; secondary, tertiary and quaternary amines.

Examples of detergent forming acids are the various fatty acids of, say, to carbon atoms,

wool fat acids, parafiin wax acids (produced by oxidation of paramn wax), chlorinated fatty acids, rosin acids, aromatic carboxylic acids including aromatic fatty acids, aromatic hydroxy fatty acids, paraffin wax benzoic acids, various then mono-esters, aromatic keto acids, aromatic ether acids; diphenols as di-(alkyl phenol) sulfides and disulfides, methylene bis alkyl phenols;

' tolized fatty or mineral oils and the like.

An excellent metallic detergent for the present purposeis the calcium salt of oil-soluble petro- Amount. a re: Additive per cent 130' 0. 140 0. 180 0. 100' 0. 170 0. critiml a corrosion temperature a 'o. 1; Non 2&1 70.0 14.5 115 v 2. oaseitoi' alky dphm oiiormsldehydeeondensatian+0a Petra eum I? OJ 4 03 aka 156460 3. Reaction Product Example I 0.1 0. 46 l. 15 30. l 100 4. Reaction Product Ex. I+Oa salt of alkyl phenol formaldehyde condensation- 1 e 0. 2 0. 13. 1. 10 0. 84 0. 49 170 tneeoti ma tf' it? :1 o i alkyl i i i-ifiiiiiid' '23- on x; a s -p eno eondensationi-Oapetro sum suiionatemn. 1 n

penta methyl-phenol, 2,4 dimethyl-d-tertiarybutyl phenol, 2,4-dimethyl-6-octyl phenol, 2,6-ditertiary-butyl-4-;methyl-pheno1, 2,4,6 tritertiarybutyl phenol and the like; aminophenols as benzyl amino phenols; amines such as dibutyl-phenylene diamine, diphenyl-amine, phenyl-beta-naphthylamine, phenyl-alpha-naphthylamine, dinaphthylamine. I

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids; organic compounds containing an acidic radical in close proximity to a nitrile, nitro or nitroso group (e. g. alpha cyano stearic acid).

Extreme pressure agents which may be used comprise: esters of phosphorus acids such as triaryl, alkyl hydroxy aryl, or aralkyl phosphates, thiophosphates or phosphites and the like; neutral leum sulfonic acids. This may be present advan- Anti oxidants comprise several types, for exam- Q aromatic sulfur compounds of relatively high boil- 7 ing temperatures such as diaryl sulfides, diaryl disulfides, alkyl aryl disulfides, e. g. diphenyl sulfide, diphenoi sulfide, dicresol sulfide, dixylenol sulfide, methyl butyl diphenol sulfide, dibenzyl sulfide, corresponding diand tri-sulfides, and the like; sulfurized fatty oils or esters of fatty acids and monohydric alcohols, e. g. sperm oil, jojoba 50 oil, etc;; in which the sulfur is strongly bonded;

sulfurized long chain olefins such as maybe obtained by dehydrogenation or cracking of wax; sulfurized phosphorized fatty oils or acids, phosphorus acid esters having sulfurized organic radicals, such as esters of phosphoric or phosphorus acids with sulfurized hydroxy fatty acids; chlorinated hydrocarbons such as chlorinated paraffin, aromatic hydrocarbons, terpenes, mineral lubricating oil, etc. or chlorinated esters of fatty o0 acids containing the chlorine in'position other than alpha position.

Additional ingredients may comprise oil-soluble urea or thio-urea derivatives, e. g. urethanes, allophanates, carbazides, carbazones, etc.; poly- 05 isobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oil-soluble compounds.

Depending upon the additive used and conditions under which it is used, the amount of additive used may vary from 0.01 to 2% or higher. However substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with phosphorus sulfide-cyclic ketone reaction products of this invention.

. It is to be understood that while theleatures 200 0., phosphorus sulfide with crude isophorone of the invention have been described and illusbottoms comprising essentially unsaturated cyclic trated in connection with certain specific examketone fractions having at least 15 carbon atoms ples, the invention, however, is not to be limited per molecule the ratio of the phosphorus sulfide thereto or otherwise restricted, except by the to the ketone compound being 1:4 to about 1:8 prior art and the scope of the appended claims. respectively.

I claim as my invention: 7. A lubricantcomprising a major amount of 1. A composition comprising a major amount of a mineral lubricating oil and a minor amount, but a liquid hydrocarbon and a minor amount, suflisufllcient to stabilize said mineral oil against decient to stabilize said liquid hydrocarbon against terioration and improve its anti-wear properties, deterioration and improve its anti-wear properof a stable, non-corrosive phosphorusand sulfurties, of a stable, non-corrosive phosphorus and containing reaction product obtained by reacting. sulfur-containing reaction product obtained by reat a temperature ranging from 130 C. to about acting, at a temperature ranging from 130 C. to 200 0., phosphorus sulfide with crude hydrolyzed about 200 C., phosphorus sulfide and a cyclic keisophorone bottoms comprising essentially untone fraction having at least 12 carbon atoms the saturated cyclic ketone fractions having at least ratio of the phosphorus sulfide to the ketone com- 15 carbon atoms per molecule the ratio ol' the pound being 1 :4 to about 1:8 respectively. phosphorus sulfide to the ketone compound being 2. A composition comprising a major amount 1:4 to about 1:8 respectively.

of a liquid hydrocarbon and a minor amount, A lubricant comprising a major amount of A sufilcient to stabilize said liquid hydrocarbon a mineral lubricating oil and a minor amount, but against deterioration and improve its anti-wear Silfiieient o Stabilize S min r l 011 against d properties, of a stable, non-corrosive hosphorusterioration and improv ts a ar prop and sulfur-containing reaction product obtained of a stable, non-corrosive'phosphorusand sulfurby reacting, at a temperature ranging from 130 containing reaction product obtained by reacting C. to about 200 C., phosphorus sulfide and satuat a p rature of from 130 C. to 200 C.. Phosrated cyclic ketone fractions having at least 12 phorus pentasulfi w un d ey ecarbon atoms the ratio of the phosphorus sulfide tone fractions having at least 12 and m re carto the ketone compound being 1:4 to about 1:3 bon atoms-and derived from the condensation of respectively. acetone to high molecular weight isophorone frac- 3. A composition comprising a maj u t of tions the ratio of the phosphorus sulfide to the a liquid hydrocarbon and a minor amount, sufketone c pound being :4 to abou r pecficient to stabilize said liquid hydrocarbon against ydeterioration and improve its anti-wear proper- A lubricant comprising a m l nt of ties, of a stable, non-corrosive phosphorusand 36 a mineral catin o a d a m nor a u t. sulfur-containing reaction product obtained by but Sliflieient to iliz sai min 011 a in reacting, at a temperature ranging from 130 c deterioration and improve its anti-wear properto about 200 0., phosphorus sulfide and t ties, of a stable, non-corrosive phosphorusand rated cyclic ketone fractions having at least 12 r-containing reaction pr d Obtained, y carbon atoms the ratio of the phosphorus sulfide 40 reacting, at a mp rature ranging from 130 C. to the ketone compound being 1:4 to about 1:8 to about phosphoras p ntasulflde with respectively. crude isophorone bottoms comprising essentially 4, A composition comprising majpr amount of unsaturated cyclic ketone fractions having at li d hydrocarbon and minor t, t, least 15 carbon atoms per molecule the ratio of sufllcient to stabilize said liquid hydrocarbon I the phoephaiils Sulfide to the k ne commune against deterioration and improve its anti-wear being 134 to about 8 respectivelyproperties, of a stable, non-corrosive phosphorus- A lubricant c mpri in a major amount of and sulfur-containing reaction product obtained a mineral lubricating oil and a min r amo n by reacting, at a temperature ranging from 130 but suillcient to stabilize said mineral oil against C. to about 200 0., phosphorus sulfide with undeterioration and improve its anti-wear propersaturated cyclic ketone fractions having at least ties- Of a e. non-corrosive phosph r and 12 carbon atoms and derived from condensation Sulfur-containing reaction P oduct O a ned y of acetone to high molecular weight isophorone reacting at a p ure 01' from 30 C. to 200 type fractions the ratio of the phosphorus sulfide a phosphorus fide w c e isophorone to the ketone compound being 1:4 to about 1:8 bottom c prising essentially unsaturated cy li respectively. ketone fractions having at least 12 carbon atoms 5. A lubricant comprising a major amount of per molecule the a o 01 e Phosphorus Sulfide a mineral lubricating oil and a minor amount, to the ketone 001119011116 being 2 o about 118 but suflicient to stabilize said nuneral oil against respectively. deterioration and improve its anti-wear proper- A lubricant c p s a ajor a ount of ties, of a stable, non-corrosive phosphorusand a al lubrica ing oil and a minor amount. sulfur-containing reaction product obtained by but suflicient to stabilize said mineral oil against reacting at a temperature ranging from 130 C. to deterioration d p e i anti-weal P pe about 200 C., phosphorus sulfide with isophorone ties. of a Stable. r ve pho ph rusand bottoms comprising essentially unsaturated cyclic 66 s u i i eaction product obtained y ketone fractions having at least 12 carbon atoms reacting at a p r ure of from 1 C. to 200 the ratio of the phosphorus sulfide to the ketone one moi Pi s w fr m ou o about 2 compound being 1:4 t bo t 1:8 t v ly. mols of unsaturated cyclic ketone fractions hav- 6. A lubricant comprising a major amount of a n at l a 2 car on atoms and derived from mineral lubricating oil and a minor amount, but 70 condensation of acetone. suificient to stabilize said mineral oil against de- 12. A lubricant comprising a major amount oi terioration and improve its anti-wear properties, a mineral lubricating oil and a minor amount, but of a stable, non-corrosive phosphorusand sulfursuflicient to stabilize said mineral oil against decontaining reaction product obtained by reacting, terioration and to improve its anti-wear properat a temperature ranging from 130 C. to about ties, of a stable, non-corrosive phosphorusand l3 sulfur-containing reaction product obtained by reacting at a temperature of from 130 C. to 200 6., one mol of Past with from about 1.3 to about 2 mols oi. crude isophorone bottoms comprising essentially unsaturated cyclic ketone fractions having more than 18 carbon atoms per molecule.

13. A lubricant comprising a major amount of a mineral lubricating oil and a minor amount, but suflicient to stabilize said mineral oil against deterioration and to improve its anti-wear properties, of a stable, non-corrosive phosphorusand sulfur-containing reaction product obtained by reacting at a temperature of from 130 C. to 200 0., one mol of P285 with from about 1.2 to about 2 mols of topped, crude isophorone bottoms comprising essentially unsaturated cyclic ketone fractions having at least carbon atoms per molecule.

14.- A lubricant comprising a major amount of a mineral lubricating oil and a minor amount, but suflicient to stabilize said mineral 011 against deterioration and to improve its anti-wear properties, of a stable, non-corrosive phosphorusand sulfur-containing reaction product obtained by reacting at a temperature of from 130 C. to 200 C., one mol of Past with from about 1.2 to about 2 mols of topped, crude hydrolyzed isophorone bottoms comprising essentially unsaturated cyclic ketone fractions having at least 15 carbon atoms per molecule.

15. A lubricant comprising a major amount of a mineral lubricating oil and a minor amount, but suillcient to stabilize said mineral oil against deterioration and to improve its anti-wear properties, of a stable, non-corrosive phosphorusand sulfur-containing reaction product obtained by reacting at a temperature of from 130 C. to 200 0., one mol of Pass with from about 1.2 to about 2 mols of crude isophorone bottoms comprising essentially unsaturated cyclic. ketone fractions having at least 12 carbon atoms, said reaction being effected at a temperature between about 150 C. and 180 C.

16. A lubricant comprising a major amount of a mineral lubricating oil ands-minor amount. but sumcient to stabilize said mineral oil against deterioration and to improve its anti-wear properties, of a stable, non-corrosive phosphorusand sulfur-containing reaction product obtained by reacting at a temperature of from 130' C. to 200 0., one mol of Fast with from about 1.2 to about 2 mols of topped, crude isophorone bottoms comprising essentially of unsaturated cyclic ketone fractions having at least 15 carbon atoms, said reaction having been eirected at a temperature of between about 150 C. and 180 C. and in substantially an inert atmosphere.

17. A process of producing a stable, non-corrosive. phosphorusand sulfur-containing reaction. product which comprises reacting a phosphorus sulfide, at an elevated temperature, with an unsaturated cyclic ketone fraction having at least 12 carbon atoms and derived from condensation of acetone to high molecular weight isophorone type fractions, said final reaction product containing above 0.82% phosphorus and above 7.7% sulfur.

18. A process of producing a stable, non-corrosive, oil-soluble lubricant additive, which comprises reacting one mol of Pass with about 1.2 to 2 mols of topped, crude isophorone bottoms comprising essentially of unsaturated cyclic ketone fractions having at least 15 and preferably more than 18 carbon atoms, at around about 160 C. and in substantially inert atmosphere, dispersing said reaction product containing both phosphorus and sulfur in an aliphatic hydrocarbon solvent, and removing the extract fraction and distilling oi! the solvent.

19. A compounded lubricant comprising a maior amount of a mineral lubricating oil, and a minor but active amount of calcium salt of alkyl phenol-formaldehyde condensation reaction product and of calcium salt of petroleum sulfonic acid as detergents, and between about 0.1% and 0.5% of an oil additive reaction product formed by the process of claim 18.

20. As a composition, a phosphorus and sulfur containing unsaturated cyclic ketone having at least 12 carbon atoms derived from the condensation of acetone, the phosphorus and sulfur content being above 0.82% and 7.7%, respectively.

21. As a composition, a phosphorus and sulfur containing unsaturated cyclic ketone having at least 12 carbon atoms, the phosphorus and sulfur content being above 0.82% and 7.7%, respectively.

'22. As a composition, a phosphorus and sulfur containing cyclic ketone having at least 12 carbon atoms, the phosphorus and sulfur content being above 0.82% and 7.7%, respectively.

MAYER B. GOREN.

REFERENCES CITED Theiollowingrefereneesareotrecordinthe file of patent:

UNITED STATES PATENTS Number Name 1 Date 2,242,280 Prutton May 20, 1941 2,383,497 Otto et a1. Aug. 28, 1945 2,419,153 Musselman et al. .Apr. 15, 1947 Bpersnsh: "J. Russ. Phys. Chem. 800.." vol. 88.. pages 1288 and 1348-1850: abstracted in Chem. Abs vol. 1 (1907). P 2118. 

